Temperature-dependent CO desorption kinetics on supported gold nanoparticles: Relevance to clean hydrogen production and fuel cell systems

The influence of the temperature on the CO desorption process was studied on supported gold nanoparticles using isotopic exchange experiments and mass spectrometric detection. CO desorption kinetics data were measured for a range of temperature from 25 to 150 °C and for a fixed CO concentration of 1000 ppm. The measured temperature-dependent kinetics data were discussed with relation to the CO tolerance issue at the proton exchange membrane fuel cell anode, the water-gas-shift and preferential CO oxidation reactions. The high measured rates of CO desorption give support to the argument that the rate of CO adsorption/desorption (and not CO electrooxidation) plays the most significant role in determining the equilibrium CO coverage at the fuel cell anode and the subsequent CO tolerance. The measured desorption rate constants are believed to be also of added value for the development of elementary reaction step-based kinetics models for the water-gas-shift and preferential CO oxidation reactions. In addition, Arrhenius parameters were calculated and their variations provided insight into the underlying adsorption/desorption processes. The influence of a temperature cycle up to 150 °C on the properties of the supported gold nanoparticles was also assessed with regard to CO desorption kinetics and catalyst nanostructure.     

Particle size dependence of CO tolerance of anode PtRu catalysts for polymer electrolyte fuel cells

An anode catalyst for a polymer electrolyte fuel cell must be CO-tolerant, that is, it must have the function of hydrogen oxidation in the presence of CO, because hydrogen fuel gas generated by the steam reforming process of natural gas contains a small amount of CO. In the present study, PtRu/C catalysts were prepared with control of the degree of Pt-Ru alloying and the size of PtRu particles. This control has become possible by a new method of heat treatment at the final step in the preparation of catalysts. The CO tolerances of PtRu/C catalysts with the same degree of Pt-Ru alloying and with different average sizes of PtRu particles were thus compared. Polarization curves were obtained with pure H₂ and CO/H₂ (CO concentrations of 500-2040 ppm). It was found that the CO tolerance of highly dispersed PtRu/C (high dispersion (HD)) with small PtRu particles was much higher than that of poorly dispersed PtRu/C (low dispersion (LD)) with large metal particles. The CO tolerance of PtRu/C (HD) was higher than that of any commercial PtRu/C. The high CO tolerance of PtRu/C (HD) is thought to be due to efficient concerted functions of Pt, Ru, and their alloy.     

Modelling CO poisoning and O2 bleeding in a PEM fuel cell anode

Fuel gas containing carbon monoxide severely degrades the performance of a polymer electrolyte membrane (PEM) fuel cell. However, CO poisoning can be mitigated by introducing oxygen into the fuel (oxygen bleeding). A mathematical PEM fuel cell model is developed that simulates both CO poisoning and oxygen bleeding, and obtains excellent agreement with published, experimental data. Modelling efforts indicate that CO adsorption and desorption follow a Temkin model. Increasing operating pressure or temperature mitigates CO poisoning, while use of reformate fuel increases the severity of the poisoning effect. Although oxygen bleeding mitigates CO poisoning, an unrecoverable performance loss exists at high current densities due to competition for reaction sites between hydrogen adsorption and the heterogeneous catalysis of CO. Copyright © 2003 John Wiley & Sons, Ltd.     

A novel proton exchange membrane fuel cell anode for enhancing CO tolerance

A novel proton exchange membrane fuel cell (PEMFC) anode which can facilitate the CO oxidation by air bleeding and reduce the direct combustion of hydrogen with oxygen within the electrode is described. This novel anode consists of placing Pt or Au particles in the diffusion layer which is called Pt- or Au-refined diffusion layer. Thus, the chemical oxidation of CO occurs at Pt or Au particles before it reaches the electrochemical catalyst layer when trace amount of oxygen is injected into the anode. All membrane electrode assemblies (MEAs) composed of Pt- or Au-refined diffusion layer do perform better than the traditionary MEA when 100 ppm CO/H₂ and 2% air are fed and have the performance as excellent as the traditionary MEA with neat hydrogen. Furthermore, CO tolerance of the MEAs composed of Au-refined diffusion layer was also assessed without oxygen injection. When 100 ppm CO/H₂ is fed, MEAs composed of Au-refined diffusion layer have the slightly better performance than traditionary MEA do because Au particles in the diffusion layer have activity in the water gas shift (WGS) reaction at low temperature.     

Two-layer anode electrode with non-noble catalysts as CO tolerant structure for PEM fuel cell

Many studies on platinum-based dual-metal or multi-metal alloys catalysts are underway to strengthen the resistance of the anode catalyst layer against hydrogen fuel contamination, especially carbon monoxide. The change in the structure of the catalyst layer can also be a new and effective way to remove Carbon Monoxide. In the few multi-layer electrode structure reported cases, ruthenium metal is used in the outer layer, for sieving the Carbon Monoxide molecules before reaching to the Pt/C catalyst in the inner layer. In this study, we make two-layer catalyst anode electrode with SnO₂/C and Sn₂₀.Co₈₀/C in outer layer and commercial Pt/C in inner layer. The performance of these electrodes for Carbon Monoxide electro-oxidation evaluate by cyclic voltammetry and the results compare with the activity of an electrode with commercial platinum catalyst only. Our two-layer electrodes have the same efficiency as commercial platinum electrodes and even more for pure hydrogen oxidation and much better activity for pure Carbon Monoxide electro-oxidation at low potentials, in half-cell media. These electrodes have better stability for Carbon Monoxide oxidation after 100 cycles along with Carbon Monoxide gas bubbling and electrode with bi-metal catalyst in outer layer has almost no loss in performance.     

Operating line analysis of fuel processors for PEM fuel cell systems

At least three different definitions of fuel processor efficiency are in widespread use in the fuel cell industry. In some instances the different definitions are qualitatively the same and differ only in their quantitative values. However, in certain limiting cases, the different efficiency definitions exhibit qualitatively different trends as system parameters are varied. In one limiting case that will be presented, the use of the wrong efficiency definition can lead a process engineer to believe that a theoretical maximum in fuel processor efficiency exists at a particular operating condition, when in fact no such efficiency optimum exists. For these reasons, the objectives of this paper are to: (1) quantitatively compare and contrast these different definitions, (2) highlight the advantages and disadvantages of each definition and (3) recommend the correct definition of fuel processor efficiency.     

Experimental evaluation of CO poisoning on the performance of a high temperature proton exchange membrane fuel cell

We experimentally studied a high temperature proton exchange membrane (PEM) fuel cell to investigate the effects of CO poisoning at different temperatures. The effects of temperature, for various percentages of CO mixed with anode hydrogen stream, on the current-voltage characteristics of the fuel cell are investigated. The results show that at low temperature, the fuel cell performance degraded significantly with higher CO percentage (i.e., 5% CO) in the anode hydrogen stream compared to the high temperature. A detailed electrochemical analysis regarding CO coverage on electrode surface is presented which indicates that electrochemical oxidation is favorable at high temperature. A cell diagnostic test shows that both 2% CO and 5% CO can be tolerated equally at low current density (<0.3 A cm⁻²) with high cell voltage (>0.5 V) at 180 °C without any cell performance loss. At high temperature, both 2% CO and 5% CO can be tolerated at higher current density (>0.5 A cm⁻²) with moderate cell voltage (0.2-0.5 V) when the cell voltage loss within 0.03-0.05 V would be acceptable. The surface coverage of platinum catalyst by CO at low temperature is very high compared to high temperature. Results suggest that the PEM fuel cell operating at 180 °C or above, the reformate gas with higher CO percentage (i.e., 2-5%) can be fed to the cell directly from the fuel processor.     

重力对PEM燃料电池性能的影响

水对质子交换膜(PEM)燃料电池的性能有极其重要的影响,良好的水管理是PEM燃料电池保持高性能的必要条件.通过试验,观察了在重力作用下液态水对PEM燃料电池性能及其内部传质的影响,分析了PEM燃料电池单体电极的不同摆放位置对其性能的影响.试验结果发现:在电流密度较小时,重力对PEM燃料电池性能的影响不明显,电流密度较大时,重力对PEM燃料电池性能的影响比较明显.试验结果对优化PEM燃料电池的结构和水管理有一定的参考价值.     

Numerical investigation of the impact of two-phase flow maldistribution on PEM fuel cell performance

Flow maldistribution usually happens in PEM fuel cells when using common inlet and exit headers to supply reactant gases to multiple channels. As a result, some channels are flooded with more water and have less air flow while other channels are filled with less water but have excessive air flow. To investigate the impact of two-phase flow maldistribution on PEM fuel cell performance, a Volume of Fluid (VOF) model coupled with a 1D MEA model was employed to simulate two parallel channels. The slug flow pattern is mainly observed in the flow channels under different flow maldistribution conditions, and it significantly increases the gas diffusion layer (GDL) surface water coverage over the whole range of simulated current densities, which directly leads to poor fuel cell performance. Therefore, it is recommended that liquid and gas flow maldistribution in parallel channels should be avoided if possible over the whole range of operation. Increasing the gas stoichiometric flow ratio is not an effective method to mitigate the gas flow maldistribution, but adding a gas inlet resistance to the flow channel is effective in mitigating maldistribution. With a carefully selected value of the flow resistance coefficient, both the fuel cell performance and the gas flow distribution can be significantly improved without causing too much extra pressure drop.     

Effects of stack orientation and vibration on the performance of PEM fuel cell

An experimental study is carried out to investigate effects of stack orientation and vibration on the performance of Proton Exchange Membrane (PEM) fuel cell. A 25‐cm² single cell with serpentine anode and straight cathode flow channels is used. The hydrogen flow rate, cathode air temperature, and relative humidity are kept constant at 60 smL/min, 20 °C and 80%, respectively, whereas the cathode air flow rate values are 220, 440, and 660 smL/min as well as free breathing case. An orientation and vibration mechanisms are designed to facilitate different values orientation positions and vibration amplitude and frequency of the stack. The results show that stack orientation and vibration have significant effects on the performance of PEM fuel cell. Based on the results obtained from this study, it can be concluded that optimum positions of cell orientation are 30° and 90° at low and high values of cathode air flow rate, respectively. Also, an improvement in the performance of the fuel cell is achieved when the stack is vibrated with low values of amplitude and frequency. Each of cell maximum power density and maximum hydrogen utilization decreases with increasing each of amplitude and frequency of stack vibration. Copyright © 2014 John Wiley & Sons, Ltd.     

Experimental and modelling studies of CO poisoning in PEM fuel cells

This article is an examination of the CO poisoning and cleaning (stripping) phenomenon that occur in a PEM fuel cell operating on an impure hydrogen stream such as reformed hydrocarbons or alcohols. A range of experimental results including cell polarization curves, measurements of spontaneous and transient oscillations of the anode potential and current pulsing behaviour are presented. Detailed examination of the pulsing process has shown that optimization of both the pulse width and pulse initiation potential will have an important impact on the overall fuel cell efficiency. To optimize these processes, the development of a mathematical model to understand and control the poisoning and cleaning processes is going to be important. In this paper, we have extended the model of Zhang et al. [J. Zhang, Investigation of CO tolerance in proton exchange membrane fuel cells, PhD thesis, Worcester Polytechnic Institute, June, 2004; J. Zhang, R. Datta, J. Electrochem. Soc. 149 (2002) A1423; J. Zhang, J.D. Fehribach, R. Datta, J. Electrochem. Soc. 151 (2004) A689] to include mass transfer effects. It is shown that this new model gives results that are in reasonable agreement with our experimental data.     

Analysis and control of a fuel delivery system considering a two-phase anode model of the polymer electrolyte membrane fuel cell stack

The fuel delivery system using both an ejector and a blower for a PEM fuel cell stack is introduced as a fuel efficiency configuration because of the possibility of hydrogen recirculation dependent upon load states.A high pressure difference between the cathode and anode could potentially damage the thin polymer electrolyte membrane. Therefore, the hydrogen pressure imposed to the stack should follow any change of the cathode pressure. In addition, stoichiometric ratio of the hydrogen should be maintained at a constant to prevent a fuel starvation at abrupt load changes.Furthermore, liquid water in the anode gas flow channels should be purged out in time to prevent flooding in the channels and other layers. The purging control also reduces the impurities concentration in cells to improve the cell performance.We developed a set of control oriented dynamic models that include a anode model considering the two-phase phenomenon and system components The model is used to design and optimize a state feedback controller along with an observer that controls the fuel pressure and stoichiometric ratio, whereby purging processes are also considered. Finally, included is static and dynamic analysis with respect to tracking and rejection performance of the proposed control.     

On the tungsten carbide synthesis for PEM fuel cell application – Problems,challenges and advantages

Fuel cell application of tungsten carbide is revisited starting with four different tungsten carbide precursors used for high temperature synthesis. It was shown that the final products greatly depend on the nature of the precursor. Using tungsten peroxide/2-propanol derived precursor almost pure WC was obtained which was subjected to further electrochemical investigation. It was shown that it is necessary to decorate WC with Pt nanoparticles in order to obtain satisfactory fuel cell performance, but catalytic activity of Pt/WC anode catalyst is not expected to overcome the activity of Pt/C. It is argued that new synthetic routes for the preparation of WC should be directed towards obtaining highly dispersed WC, that is, WC with high external surface area available for Pt deposition, rather than high specific surface area WC with large contribution of micropores having no importance when it comes to the use of WC as a catalyst support. The true benefit of the use of WC as catalyst support is found in increased CO tolerance/CO oxidation activity of WC-supported Pt catalysts. Qualitative mechanistic view on increased CO oxidation activity of Pt/WC is offered.     

Effects of fuel cell anode recycle on catalytic fuel reforming

The presence of steam in the reactant gas of a catalytic fuel reformer decreases the formation of carbon, minimizing catalyst deactivation. However, the operation of the reformer without supplemental water reduces the size, weight, cost, and overall complexity of the system. The work presented here examines experimentally two options for adding steam to the reformer inlet: (I) recycle of a simulated fuel cell anode exit gas (comprised of mainly CO₂, H₂O, and N₂ and some H₂ and CO) and (II) recycle of the reformate from the reformer exit back to the reformer inlet (mainly comprised of H₂, CO, and N₂ and some H₂O and CO₂). As expected, anode gas recycle reduced the carbon formation and increased the hydrogen concentration in the reformate. However, reformer recycle was not as effective due principally to the lower water content in the reformate compared to the anode gas. In fact, reformate recycle showed slightly increased carbon formation compared to no recycle. In an attempt to understand the effects of individual gases in these recycle streams (H₂, CO, CO₂, N₂, and H₂O), individual gas species were independently introduced to the reformer feed.     

阴极流道分流进气对燃料电池性能影响的实验研究

针对高工作电流密度下,燃料电池内局部水淹导致的传质损失问题,本研究提出了一种阴极流道多进口分流进气方式。实验研究了三种典型分流口位置及分流进量对电池性能的影响。研究发现随着分流口远离阴极主进气口,电池性能呈现先上升后下降的趋势,且当分流口靠近主进气口时,增加分流量有助于电池性能提升,但分流量的增加对电池性能的提升存在一个极限值;因此,在对电池进行分流进气优化时需综合考虑分流口位置和分流量的影响。当分流口为SIP-30%且分流量为按化学当量比ξc = 0.75取值时,分流进气方式相比传统进气方式,电池的最大功率密度高出17.8%。     

Development of paper-structured catalyst for application to direct internal reforming solid oxide fuel cell fueled by biogas

A flexible paper-structured catalyst (PSC) that can be applied to the anode of a solid oxide fuel cell (SOFC) was examined for its potential to enable direct internal reforming (DIR) operation. The catalytic activity of three types of Ni-loaded PSCs: (a) without the dispersion of support oxide particles in the fiber network (PSC-A), (b) with the dispersion of (Mg,Al)O derived from hydrotalcite (PSCB), and (c) with the dispersion of (Ce,Zr)O_2-δ (PSCC), for dry reforming of CH₄ was evaluated at operating temperatures of 650–800 °C. Among the PSCs, PSC-C exhibited the highest CH₄ conversion with the lowest degradation rate. The electrochemical performance of an electrolyte-supported cell (ESC) was evaluated under the flow of simulated biogas at 750 °C for cases without and with the PSCs on the anode. The application of the PSCs improved the cell performance. In particular, PSC-C had a remarkably positive effect on stabilizing DIRSOFC operation fueled by biogas.     

Effect of sub-freezing temperatures on a PEM fuel cell performance, startup and fuel cell components

The cold-start behavior and the effect of sub-zero temperatures on fuel cell performance were studied using a 25-cm² proton exchange membrane fuel cell (PEMFC). The fuel cell system was housed in an environmental chamber that allowed the system to be subjected to temperatures ranging from sub-freezing to those encountered during normal operation. Fuel cell cold-start was investigated under a wide range of operating conditions. The cold-start measurements showed that the cell was capable of starting operation at −5 °C without irreversible performance loss when the cell was initially dry. The fuel cell was also able to operate at low environmental temperatures, down to −15 °C. However, irreversible performance losses were found if the cell cathode temperature fell below −5 °C during operation. Freezing of the water generated by fuel cell operation damaged fuel cell internal components. Several low temperature failure cases were investigated in PEM fuel cells that underwent sub-zero start and operation from −20 °C. Cell components were removed from the fuel cells and analyzed with scanning electron microscopy (SEM). Significant damage to the membrane electrode assembly (MEA) and backing layer was observed in these components after operation below −5 °C. Catalyst layer delamination from both the membrane and the gas diffusion layer (GDL) was observed, as were cracks in the membrane, leading to hydrogen crossover. The membrane surface became rough and cracked and pinhole formation was observed in the membrane after operation at sub-zero temperatures. Some minor damage was observed to the backing layer coating Teflon and binder structure due to ice formation during operation.     

Modelling of proton exchange membrane fuel cell performance based on semi-empirical equations

Using semi-empirical equations for modeling a proton exchange membrane fuel cell is proposed for providing a tool for the design and analysis of fuel cell total systems. The focus of this study is to derive an empirical model including process variations to estimate the performance of fuel cell without extensive calculations. The model take into account not only the current density but also the process variations, such as the gas pressure, temperature, humidity, and utilization to cover operating processes, which are important factors in determining the real performance of fuel cell. The modelling results are compared well with known experimental results. The comparison shows good agreements between the modeling results and the experimental data. The model can be used to investigate the influence of process variables for design optimization of fuel cells, stacks, and complete fuel cell power system.     

Basic properties of a liquid tin anode solid oxide fuel cell

An unconventional high temperature fuel cell system, the liquid tin anode solid oxide fuel cell (LTA-SOFC), is discussed. A thermodynamic analysis of a solid oxide fuel cell with a liquid metal anode is developed. Pertinent thermochemical and thermophysical properties of liquid tin in particular are detailed. An experimental setup for analysis of LTA-SOFC anode kinetics is described, and data for a planar cell under hydrogen indicated an effective oxygen diffusion coefficient of 5.3 × 10⁻⁵ cm² s⁻¹ at 800 °C and 8.9 × 10⁻⁵ cm² s⁻¹ at 900 °C. This value is similar to previously reported literature values for liquid tin. The oxygen conductivity through the tin, calculated from measured diffusion coefficients and theoretical oxygen solubility limits, is found to be on the same order of that of yttria-stabilized zirconia (YSZ), a traditional SOFC electrolyte material. As such, the ohmic loss due to oxygen transport through the tin layer must be considered in practical system cell design since the tin layer will usually be at least as thick as the electrolyte.